CN113142228A - Bactericide composition - Google Patents
Bactericide composition Download PDFInfo
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- CN113142228A CN113142228A CN202011134207.XA CN202011134207A CN113142228A CN 113142228 A CN113142228 A CN 113142228A CN 202011134207 A CN202011134207 A CN 202011134207A CN 113142228 A CN113142228 A CN 113142228A
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- QPHVQMSISUVMAP-UHFFFAOYSA-N prop-2-enoic acid;quinoline Chemical compound OC(=O)C=C.N1=CC=CC2=CC=CC=C21 QPHVQMSISUVMAP-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- YRRBXJLFCBCKNW-UHFFFAOYSA-N prothiocarb Chemical compound CCSC(=O)NCCCN(C)C YRRBXJLFCBCKNW-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- KKEJMLAPZVXPOF-UHFFFAOYSA-N pyraziflumid Chemical compound C1=C(F)C(F)=CC=C1C1=CC=CC=C1NC(=O)C1=NC=CN=C1C(F)(F)F KKEJMLAPZVXPOF-UHFFFAOYSA-N 0.000 description 1
- JOOMJVFZQRQWKR-UHFFFAOYSA-N pyrazophos Chemical compound N1=C(C)C(C(=O)OCC)=CN2N=C(OP(=S)(OCC)OCC)C=C21 JOOMJVFZQRQWKR-UHFFFAOYSA-N 0.000 description 1
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 description 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical class OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 1
- DEIKMOQTJBGGAX-DJKKODMXSA-N pyriminobac Chemical compound CO\N=C(/C)C1=CC=CC(OC=2N=C(OC)C=C(OC)N=2)=C1C(O)=O DEIKMOQTJBGGAX-DJKKODMXSA-N 0.000 description 1
- 229960002026 pyrithione Drugs 0.000 description 1
- 229960003811 pyrithione disulfide Drugs 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- MRUMAIRJPMUAPZ-UHFFFAOYSA-N quinolin-8-ol;sulfuric acid Chemical compound OS(O)(=O)=O.C1=CN=C2C(O)=CC=CC2=C1 MRUMAIRJPMUAPZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical compound OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 description 1
- 229950000975 salicylanilide Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000003620 semiochemical Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010294 sodium orthophenyl phenol Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000021012 strawberries Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- LWLJEQHTPVPKSJ-UHFFFAOYSA-N tebufloquin Chemical compound C1=C(C(C)(C)C)C=C2C(OC(=O)C)=C(C)C(C)=NC2=C1F LWLJEQHTPVPKSJ-UHFFFAOYSA-N 0.000 description 1
- ROZUQUDEWZIBHV-UHFFFAOYSA-N tecloftalam Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)NC1=CC=CC(Cl)=C1Cl ROZUQUDEWZIBHV-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 description 1
- ILERPRJWJPJZDN-UHFFFAOYSA-N thioquinox Chemical compound C1=CC=C2N=C(SC(=S)S3)C3=NC2=C1 ILERPRJWJPJZDN-UHFFFAOYSA-N 0.000 description 1
- OBZIQQJJIKNWNO-UHFFFAOYSA-N tolclofos-methyl Chemical compound COP(=S)(OC)OC1=C(Cl)C=C(C)C=C1Cl OBZIQQJJIKNWNO-UHFFFAOYSA-N 0.000 description 1
- RSOBJVBYZCMJOS-CYBMUJFWSA-N tolprocarb Chemical compound FC(F)(F)COC(=O)N[C@@H](C(C)C)CNC(=O)C1=CC=C(C)C=C1 RSOBJVBYZCMJOS-CYBMUJFWSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- IQGKIPDJXCAMSM-UHFFFAOYSA-N triazoxide Chemical compound N=1C2=CC=C(Cl)C=C2[N+]([O-])=NC=1N1C=CN=C1 IQGKIPDJXCAMSM-UHFFFAOYSA-N 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N trichlopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
- XBRCDWHXULVEFB-UHFFFAOYSA-N triphenyltin(1+) Chemical compound C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 XBRCDWHXULVEFB-UHFFFAOYSA-N 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000004552 water soluble powder Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a bactericide composition, which comprises the following compounds as active components: a compound A: 4-chloro-2- (1, 1-dimethylethyl) -5- [ [ [4- (1, 1-dimethylethyl) phenyl ] methyl ] thio ] -3(2H) -pyridazinone; and compound B: wuyimycin; the mass ratio of the compound A to the compound B is 1:10-10: 1. According to the invention, the compound A and the compound B are compounded, and the obtained composition has an excellent control effect. Meanwhile, the composition expands the bactericidal spectrum, has a synergistic effect, can improve the disease control effect, enables germs to be difficult to generate drug resistance, and can be used for controlling downy mildew, late blight, epidemic disease, damping-off, powdery mildew, rust disease, anthracnose and the like on vegetables such as cucumbers, cabbages, spinaches, hot peppers, tomatoes and the like, and crops such as potatoes, grapes, oranges, bananas and the like, as well as soybean root rot, tobacco leaf black shank and the like.
Description
Technical Field
The invention belongs to the field of agricultural bactericides and particularly relates to a bactericide composition.
Background
Downy mildew, powdery mildew and epidemic diseases are common diseases of melons, fruit trees, vegetables and other crops, seriously affect the yield and quality of products and often become destructive diseases.
Downy mildew is a plant disease caused by downy mildew among fungi. Downy mildew occurs in all stages from seedling to harvest, and is seriously damaged by adult plants. Mainly harmful leaves, develop from the base to the upper leaves. At the early stage of the disease, pale yellow approximately round and polygonal scabs are formed on the leaf surfaces, and when the air is moist, frost-like mildew layers are formed on the leaf backs and can spread to the leaf surfaces. The late stage disease spot withered and dead connected tablet is yellow brown, and all outer leaves are withered and yellow to die when the disease spot is serious. The germs live through the winter by hypha on the seeds or on the vegetables in autumn and winter, and also live through the winter by oospores on the disease residues. Mainly through air flow, watering, farming and insect transmission. The germination temperature of the germ spores is 6-10 ℃, and the suitable infection temperature is 15-17 ℃. The diseases are easy to occur such as over-dense field planting, early watering, overlarge watering, high soil humidity, poor drainage and the like after field planting. In late spring, early summer or autumn, continuous rainy weather is the most likely to occur, and when the disease is serious, 20% -40% of yield loss can be caused.
Powdery mildew is a plant disease caused by the powdery mildew family (erysiphaceae) of fungi. For example: cereal powdery mildew caused by Ery-sipheredamis; powdery mildew of various plants such as melons, beans and hemp caused by cocklebur monofilament shells (sphaerotheca auricularia); grape powdery mildew caused by the grape devil's claw (Uncinula necator); powdery mildew of more than 80 trees such as mulberry, pear, persimmon, walnut, chestnut, lychee, papaya and the like caused by hazelnut ball needle shells (Phyllanticia cordifolia); powdery mildew of rose flowers caused by rose single-filament shells (sphaerothecapanannosa), and the like. In the aspect of preventing and treating powdery mildew, the traditional Chinese medicine composition mainly depends on imidazoles, triazoles, methoxyacrylates and other bactericides. These agents have developed various degrees of resistance to drugs by long-term use, and the preventive effect is reduced. In addition, triazole drugs have an inhibitory effect on the growth of crops at a high dosage, and are likely to cause phytotoxicity.
Epidemic diseases mainly refer to a kind of diseases caused by Phytophthora (Phytophthora) fungi, and mainly cause rapid necrosis and rot of tissues of flowers, fruits and leaves of plants. High humidity is a major factor affecting disease occurrence and spread. Wherein, the pepper epidemic disease, the melon epidemic disease and the potato late blight are more important diseases.
At present, the medicaments for preventing and treating downy mildew, powdery mildew and epidemic diseases mainly comprise propineb, cymoxanil, dimethomorph, flumorph, chlorothalonil, metalaxyl, fluazinam, fluopicolide and benthiavalicarb-isopropyl.
The medicament for preventing downy mildew, powdery mildew and epidemic diseases generates different degrees of medicament resistance after long-term use, the prevention and treatment effect is reduced, and the single application dosage is larger and larger. Meanwhile, the pesticide residue is increased by using a large amount of the pesticide. Endanger the food safety and aggravate the environmental pollution. Therefore, the compounding of bactericides with different action mechanisms is the development need of scientific and reasonable medication.
Through research, the compound A, namely 4-chloro-2- (1, 1-dimethylethyl) -5- [ [ [4- (1, 1-dimethylethyl) phenyl ] methyl ] thio ] -3(2H) -pyridazinone is found to have good control effect on downy mildew, late blight, epidemic disease, damping-off, powdery mildew, rust disease, anthracnose, root rot, phytophthora parasitica and the like of vegetables, fruits and field crops. In order to avoid the defect of drug resistance caused by single use, the compound A and bactericides with different action mechanisms are reasonably mixed, so that the synergistic effect is remarkable, the control effect is improved, the application times and the dosage are reduced, the generation of germ resistance is avoided, the generation speed of the drug resistance is delayed, and the problems of resistance and the like in the application process of a single pesticide can be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a bactericide and a composition thereof, which can obviously improve the control effect, reduce the application times and the dosage, help to avoid the generation of germ resistance and delay the generation speed of drug resistance, and can solve the problems of resistance and the like in the application process of a single pesticide.
In order to solve the technical problems, the invention adopts the following technical scheme:
a bactericide which comprises a compound A as an active ingredient, wherein the compound A is 4-chloro-2- (1, 1-dimethylethyl) -5- [ [ [4- (1, 1-dimethylethyl) phenyl ] methyl ] thio ] -3(2H) -pyridazinone.
A fungicide composition comprising, as active ingredients, in synergistically effective amounts:
1) a compound A: 4-chloro-2- (1, 1-dimethylethyl) -5- [ [ [4- (1, 1-dimethylethyl) phenyl ] methyl ] thio ] -3(2H) -pyridazinone; and 2) at least one active compound B selected from the group consisting of:
n-butylamine (butylamine); cymoxanil (cymoxanil); cymoxanil (cymoxanil); dodine (dodine); biguanide salts (guazatine); iminoctadine acetate (iminoctadine); benalaxyl (benalaxyl); Benalaxyl-M (Benalaxyl-M); benodanil (benodanil); phenylhydroxamic acid (benzohydroxamic acid); n- (3', 4' -dichloro-5-fluorobiphenyl-2-yl) -3- (difluoromethyl) -1-methylpyrazole-4-carboxamide (bixafen); carboxin; carpropamid (carpropamid); diammine (chloreniformethane); cyclanilide (cyclafuramid); cyflufenamid (cyflufenamid); bensulam (dichlofluanid); diclocyanamide (diclocymet); dimethomorph (dimethomorph); methylfuroamide (fenfuram); fenhexamid (fenhexamid); fenoxanil (fenoxanil); (3S,6S,7R,8R) -8-benzyl-3- {3- [ (isobutyryloxy) methoxy ] -4-methoxypyridine-2-carboxamido } -6-methyl-4, 9-dioxo-1, 5-dioxononan-7-yl isobutyrate (fenpicoamid); fludioxonil (fludioxonil); bifena fluoride (flumetover); flumorph (flumorph); fluopicolide (fluopicolide); fluopicolide (fluopicolipkd); fluoride ether carboxamide (fluopiomide); fluopyram (fluopyram); flusulfamide (fluusfamide); flutolanil (flutolanil); furalaxyl (furalaxyl); furametpyr (furametpyr); difuranamide (furcrarbanil); fenpyrad (furmeclocox); n- [1, 1-dimethyl-2- (4-isopropoxy-o-tolyl) -2-oxoethyl ] -3-methylthiophene-2-carboxamide (isoflutamide); (RS) -2-methoxy-N-methyl-2- [ α - (2, 5-dimethylphenoxy) -o-tolyl ] acetamide (mangestolide); mandipropamid (mandipropamid); ortho-amides (mebenil); propoxybutylamine (mepronil); metalaxyl (metalaxyl); metalaxyl-M; furametpyr (methfuroxam); methylfuroamide (ofarace); oxycarboxin; penflufen (penflufen); penthiopyrad (penthiopyrad); pyranyl (pyracarbolid); (Z) -N- {2- [ 3-chloro-5- (cyclopropylethynyl) -2-pyridinyl ] -2- (isopropoxyimino) ethyl } -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide (pyrapropofol); [ N- (3', 4' -difluorobiphenyl-2-yl) -3- (trifluoromethyl) pyrazine-2-carboxamide ] (pyraziflumumid); quinone diazide (quinazamid); salicylanilide (salicilanilide); sedaxane; silthiopham (silthiofam); leaf cumylphthalein (tecloftalam); thifluzamide (thifluzamide); tiadinil (tiadinil); thiocyanobenzamide (tioxymid); sulfentram (tolnifanide); tolfluanid (tolyfluanid); trichlamide (trichlamide); triforine (triforine); propamocarb (valifenate); imazamine (vangard); cyanamide (zarilamid); zoxamide (zoxamide); gold enzyme (aureofungin); blasticidin (blasticidin S); cycloheximide (cycloheximide); griseofulvin (griseofulvin); kasugamycin (kasugamycin); moroxydine (moroxydine); myxothiazoles (myxothiazol); natamycin (natamycin); polyoxins (polyoxins); polyoxins (polyoxorim); streptomycin (streptomycin); validamycin (validamycin); biphenyl (biphenyl); chloronitronaphthalene (chlorodinitrononapthalenes); (ii) chloroneb; chlorothalonil (chlorothalonil); guaiacol (cresol); niclosamide (dicloran); phenol cycloheximide (fenjuntong); hexachlorobenzene (hexachlorobenzene); pentachlorophenol (pentachlorophenol); pentachloronitrobenzene (quintozene); sodium pentachlorophenate (sodium pentachlorophenate); tetrachloronitrobenzene (tecnazene); thiocyanatodinitrobenzenes (thiocyanatodinobenzenes); pyrimidinones (pyriofenonenes); metrafenone (metrafenone); thiophanate-methyl (thiophanate-methyl); thiophanate-methyl (thiophanate-methyl); benfurazone (furophanate); benthiavalicarb-isoproyl; blasticidin (chlorothiazole); bifidobacterium bifidum (dichlobentiazox); probenazole (probenazole); benthiavalicarb-isoproyl; blasticidin (chlorothiazole); bifidobacterium bifidum (dichlobentiazox); benfurazone (furophanate); probenazole (probenazole); thiophanate-methyl (thiophanate-methyl); diethofencarb (diethofencarb); iodopropynyl butylcarbamate (iodocarb); iprovalicarb or iprovalicarb; (6- { [ (Z) - (methyl-1H-5-tetrazolyl) (phenyl) methylene ] aminooxymethyl } -2-pyridyl) carbamic acid tert-butyl ester (picarbtrazox); propamocarb (propamocarb); thionocarb (prothiocarb); 2, 2, 2-trifluoroethyl (S) - [ 2-methyl-1- (p-toluamidomethyl) propyl ] carbamate (tolprocarb); maneb (maneb); metiram (metiram); zinofuranate (polycarbomate); zineb (zineb); ambam (amobam); oxidized thiram (azithiram); morcarb (carbamorphh); dazomet (dazomet); disulfiram (disulfiram); metem; ferbam; mancozeb (mancozeb); metam (metam); metiram (milneb); sodium metiram (nabam); propineb (propineb); sulfur substituted (tecoram); thiram (thiram); imazalil (imazalil); oxaimidazole (oxpoconazole); imazalil (S-imazalil) with high efficiency; triflumizole (triflumizole); climbazole (climbazole); clotrimazole (clotrimazole); fenamidone (fenamidone); fenapanil (fenapanil); fuberidazole (fuberidazole); chloroxidin (glyodin); pefurazoate (pefurazoate); prochloraz (prochloraz); thiabendazole (thiabendazole); imidazoxazine (triazoxide); albendazole (albendazole); benomyl (benomyl); carbendazim (carbendazim); 2- (2-chlorophenyl) -1H-benzimidazole-2 (chlorofenazole); cyhalonil (cypendazole); debacarb; methyl N- [ methyl 1- (2-methylthioethylcarbamoyl) benzimidazol-2-yl) carbamate (mecarbizid); pyrazole (rabenzazole); ametoctradin (ametoctradin); amisulbrom (amisulbrom); bitertanol (bitertanol); bromuconazole (bromuconazol); cyproconazole (cyproconazole); difenoconazole (difenoconazole); diniconazole (diniconazole); epoxiconazole (epoxiconazole); (ii) epoxiconazole (etaconazole); fenbuconazole (fenbuconazole); trifluorobenzene azole (fluotrimazole); fluquinconazole (fluquinconazole); flusilazole (flusilazole); flutriafol (flutriafol); furconazole (furconazol); furconazole (furconazol-cis); hexaconazole (hexaconazole); imibenconazole (imibenconazole); ipconazole (ipconazole); isofluconazole (ipfentrifluconazole); mefenflurazole (mefentrifluconazole); metconazole (metconazole); myclobutanil (myclobutanil); penconazole (penconazol); propiconazole (propiconazole); prothioconazole (prothioconazole); simeconazole (simeconazole); tebuconazole (tebuconazole); tetraconazole (tetraconazole); triadimefon (triadimifon); triadimenol (triadiminol); leaf rust (triazbutil); triticonazole (triticonazole); uniconazole (uniconazole); uniconazole (uniconazole-P); famoxadone (famoxadone); hymexazol (hymexazol); cyazofamid (cyazofamid); oxadixyl (oxadixyl); pyrisoxazole (acetoxazole); hydralazinone (drazoxolon); hydrazinooxazolone (metazoxolon); oxathiapiprolin (oxathiapirolin); vinclozolin (vinclozolin); copper octadecanoate (ypetacs-hopper); basic copper carbonate (basic copper carbonate); basic copper sulfate (basic copper sulfate); bordeaux mixture (bordeaux mixture); sodium carbonate bordeaux mixture (burgundy mixture); cushing mix (chestun texture); copper acetate (copper acetate); copper hydroxide (copper hydroxide); copper naphthenate (copper naphthenate); copper oleate (copper oleate); copper oxychloride (copper oxychloride); copper silicate (copper silicate); copper sulfate (copper sulfate); copper zinc chromate (copper zinc chromate); copper nonyl phenolsulfonate (cuppric nonyl phenolsulfonate); copper chloride thiram (cuprobam); cuprous oxide (cupreus oxide); mancopper; oxine-copper (oxine-copper); captafol (captafol); captan (captan); ethiprole (chlorozolinate); sclerotium (dichlozoline); dimethachlon; folpet (folpet); iprodione (iprodione); fenamiphrone (isovaledione); myclozolin (mycozolin); procymidone (procymidone); thiochlorophenylimine (thiochlorofenthim); binapacryl (binapacryl); dinobactam (dinobuton); dinocap (dinocap); enemy (dinocoton); nitryl ester (dinopenton); nitrooctyl ester acaricides (dinosulfon); nitrobutyl ester (dinoterbon); dinitrophenol (DNOC); demodiclodol (meptyldinocap); carbon disulfide (carbon disulfide); dimethyl disulfide (dimethyl disulfide); methyl bromide (methyl bromide); methyl iodide (methyl iodide); sodium thiocarbonate (sodium thiophanate); quinone oxime hydrazone (benzoquinone); sulfur (sulfur); 4-dodecyl-2, 6-dimethylmorpholine (aldimorph); bacteriostatic quinoline (benzamorf); dodecamorphol (dodemorph); fenpropimorph (fenproxorphh); tridemorph (tridemorph); aminopropanophosphoric acid (ampropylfos); sterile phosphorus (ditalimfos); fenoxanil (EBP); kewensan (edifenphos); phycomycetin phosphate (fosetyl); fosetyl-Aluminum (fosetyl-Aluminum); cyclohexaphos (hexylthiofos); fenfurazon (inezin); iprobenfos (iprobenfos); seed soaking phosphorus (izopamfos); chlorophosphine (phosdiphen); phosphorous acid (Phosphorous acid) and salts thereof; fenamiphos (pyrazophos); tolclofos-methyl; wialofos (triamiphos); decaphosphorus tin (decafentin); fentin-acetate (fentin-acetate); triphenyltin (fentin); tributyltin oxide (tributyltin oxide); barium polysulfide (barium polysulfide); lime sulfur (calcium polysulfide); potassium polysulfide (potassium polysulfide); sodium polysulfide (sodium polysulphide); benzovindiflupyr (benzovindiflupyr); fenpyrazamine (fenpyrazamine); fluxapyroxad; 3- (difluoromethyl) -N- [ (R) -2, 3-dihydro-1, 1, 3-trimethyl-1H-inden-4-yl ] -1-methylpyrazole-4-carboxamide (inpyrfluxam); n- (5-chloro-2-isopropylbenzyl) -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (isofluroxypram); isopyrazam (isopyrazam); pydiflumetofen; pyraoxystrobin (pyraoxystrobin); 3-chloro-4- (2, 6-difluorophenyl) -6-methyl-5-phenylpyridazine (pyridichloromethyl); 4-phenoxybenzyl 2-amino-6-methylnicotinate (aminopyrifen); boscalid (boscalid); sulfopyrimethanil (bupirimate); buthiopyridine (buthiobate); pyrithione (dipyrithione); fluazinam (fluazinam); pyrimethanil (peip); pyribencarb (pyribencarb); pyridine nitrile (pyridine); pyrifenox (pyrifenox); pyrisoxazole (pyrisoxazole); picolyl (pyroxychlor); chloropyrifural ether (pyroxyfur); cyprodinil (cyprodinil); flufenamid (diflumetorim); methiridine (dimethirimol); ethirimol (ethirimol); isopimatol (fenarimol); pyriminobac (ferimzone); mepanipyrim (mepanipyrim); fluoropyrimidinol (nuarimol); pyrimethanil (pyrimethanil); pyrimethanil (triarimol); fenpiclonil (fenpiclonil); chlorothalonil (fluoroimide); 8-hydroxyquinoline (8-hydroxyquinoline sulfate); tetrachloro para-quinone (chloranil); dichloronaphthoquinone (dichlone); dithianon (dithianon); ethoxyquinoline (ethoxyquin); quinoline acrylate (halacrinate); 2[2- (7-8-difluoro-2-methylquinolin-3-oxy) -6-fluorophenyl ] propanol-2-ol (ifluorequiquin); proquinazine (proquinazid); 1- (8-hydroxy-5-quinoline) ethanone (quinacetol); 4, 4-difluoro-3, 3-dimethyl-1-quinolin-3-isoquinoline (quinofumelin); phenoxyquinoline (quinoxyfen); isobutoxyquinoline (tebufloquin); quinolone (chinomethionat); tetrachloroquinoxaline (chloroquinox); acaricidal (thioquinox); thienson copper (saisentong); copper thiodiazole-coater; zinc thiazole (zinc thiazole); thiocyanobenzene (benthiazole); bismertizol (bismertizol); ethaboxam (ethaboxam); terrazole (etridiazole); isotianil (isotianil); tiadinil (metsulfovax); octulone (octhialinone); metolachlor (bentaluron); pencycuron (pencycuron); acetylcholinesterase-zinc (acetylcholinesterase-zinc); thiabendazole (cufraneb); polyoxin D zinc salt (polyoxorim-zinc); zinc naphthanate (zinc naphthanate); zinc trichlorophenoxide (zinc trichlorophenoxide); ziram; thiochlorophene (bithionol); dichlorophenol (dichlorophen); diphenylamine (diphenylamine); hexachlorophene (hexachlorophene); chloropyridine (paronol); toluoyl chrysotoxin (coumethosyntrobin); coumoxystrobin (coumoxystrobin); dimoxystrobin (dimoxystrobin); enestroburin (enestroburin); fenaminstrobin (fenaminstrobin); flufenacet (flufenoxystrobin); fluoxastrobin (fluoxastrobin); kresoxim-methyl (kresoxim-methyl); metominostrobin (metominostrobin); orysastrobin (orysastrobin); picoxystrobin (picoxystrobin); pyraclostrobin (pyraclostatin); pyraclostrobin (pyrametostatin); nitrapyrin methyl (triclopyr); trifloxystrobin (trifloxystrobin); thiabendazole (saijunmao); isoprothiolane (isoprothiolane); thiadifuro (thiadifuro); chlorothiazole nitrile (fluthial); allicin (allicin); berberine (berberine); carvacrol (carvacrol); carvone (carvone); osthole (osthol); sanguinarine (sanguinarine); santonin (santonin); n- (4' -bromobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide; n- (4' -trifluoromethyl-biphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide; 4-difluoromethyl-2-methylthiazole-5-carboxylic acid N- (4 '-chloro-3' -fluorobiphenyl-2-yl) -amide; n- (3', 4' -dichloro-4-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4-carboxamide; n- (3', 4' -dichloro-5-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4-carboxamide; 3, 4-dichloro-N- (2-cyanophenyl) isothiazole-5-carboxamide; n- (2- {4- [3- (4-chlorophenyl) prop-2-ynyloxy ] -3-methoxyphenyl } ethyl) -2-methanesulfonylamino-3-methylbutanamide; n- (2- {4- [3- (4-chlorophenyl) -prop-2-ynyloxy ] -3-methoxyphenyl } ethyl) -2-ethanesulfonylamino-3-methylbutanamide; thiadiazolyl (acibenzolar-S-methyl); wuyiencin (astromicin); benziothiazolinone (benziothiazolinone); brassinolide (brassinolide); chlormequat chloride (chlormequat); gibberellins (gibberellin); biguanide trioctylphenyl sulfonate (iminoctadine trialbisilate); oxolinic acid (oxolinic acid); prohexadione (prohexadione) and salts thereof; 2-aminobutane (sec-Butylamine); sodium o-phenylphenol (sodium o-phenylphenol oxide); trinexapac-ethyl (trinexapac-ethyl); triforine (triforine);
the mass ratio of the active component 1) to the active component 2) is 1:100-100: 1.
The content of the single agent of the compound A is 0.1-95.
Preferably, the active component 2) is at least one active compound B selected from the group consisting of:
bitertanol (bitertanol); bromuconazole (bromuconazol); difenoconazole (difenoconazole); diniconazole (diniconazole); flusilazole (flusilazole); flutriafol (flutriafol); hexaconazole (hexaconazole); myclobutanil (myclobutanil); penconazole (penconazol); propiconazole (propiconazole); prothioconazole (prothioconazole); simeconazole (simeconazole); tebuconazole (tebuconazole); tetraconazole (tetraconazole); triflumizole (triflumizole); cyproconazole (cyproconazole); epoxiconazole (epoxiconazole); fluquinconazole (fluquinconazole); triadimenol (triadiminol); imazalil (imazalil); oxaimidazole (oxpoconazole); famoxadone (famoxadone); fluazinam (fluazinam); pyrisoxazole (Acetoxazole); desmomethion (chinomethionat); proquinazine (proquinazid); phenoxyquinoline (quinoxyfen); ametoctradin (ametoctradin); cyproconazole (cyproconazole); epoxiconazole (epoxyconazole); fluquinconazole (fluquinconazole); cyclopentazolol (ipconazole); metconazole (metconazole); triadimefon (triadimifon); triadimenol (triadiminol); penconazole (triticonazole); prochloraz (prochloraz); imazalil (imazalil); benomyl (benomyl); carbendazim (carbendazim); thiabendazole (thiabendazole); fuberidazole (fuberidazole); clomazole (etridiazole); hymexazole (hymexazole); epoxiconazole (azaconazol); highly effective diniconazole (diniconazole); fenbuconazole (fenbuconazole); ipconazole (ipconazole); metconazole (metconazole); tetraconazole (tetraconazole); triticonazole (triticonazole); imazalil (imazalil); pefurazoate (pefurazoate); hymexazol (hymexazol); terrazole (etridiazole); octulone (octhialinone); thiocyanobenzene (benthiazole); dithianon (dithianon); ethoxyquinoline (ethoxyquin); hydroxyquinoline (hydroxyquinoline sulfate); myxothiazoles (myxothiazol); bismertizol (bismertizol); probenazole (probenazole); uniconazole (uniconazole-P); uniconazole (uniconazole); furconazole (furconazol-cis); furconazole (furconazol); (ii) epoxiconazole (etaconazole); leaf rust (triazbutil); trifluorobenzene azole (fluotrimazole); climbazole (climbazole); clotrimazole (clotrimazole); isofluconazole (ipfentrifluconazole); mefenflurazole (mefentrifluconazole); flumorph (flumorph); dimethomorph (dimethomorph); chlorothalonil (chlorothalonil); mancozeb (mancozeb); cymoxanil (cymoxanil); cyazofamid (cyazofamid); fluopicolide (picobenzamid); propamocarb (propamocarb); metalaxyl (metalaxyl); famoxadone (famoxadone); benziothiazolinone (benziothiazolinone); zoxamide (zoxamide); pyraclostrobin (pyraclostrobinin); azoxystrobin (azoxystrobin); oxathiapiprolin (oxathiapirolin); aluminum ethyl phosphate (fosetyl aluminum); copper nonyl phenolsulfonate; propineb (propineb); zineb (zineb); enestroburin (enestroburin); bupirimate (enestroburin); ethirimol (ethirimol); kresoxim-methyl (kresoxim-methyl); isopyrazam (isopyrazam); fluxapyroxad (fluxapyroxad); boscalid (boscalid); biguanide trioctylphenyl sulfonate (iminoctadine trialbisilate); polyoxins (polyoxins); wuyiencin (astromicin); berberine (berberine); thiophanate methyl (thiophanate methyl); mandipropamid (mandipropamid).
Preferably, the active component 2) is at least one active compound B selected from the group consisting of:
flusilazole (flusilazole); flutriafol (flutriafol); myclobutanil (myclobutanil); propiconazole (propiconazole); tebuconazole (tebuconazole); epoxiconazole (epoxiconazole); triadimefon (triadimifon); carbendazim (carbendazim); hymexazol (hymexazol); flumorph (flumorph); dimethomorph (dimethomorph); chlorothalonil (chlorothalonil); mancozeb (mancozeb); cymoxanil (cymoxanil); cyazofamid (cyazofamid); fluopicolide (picobenzamid); propamocarb (propamocarb); metalaxyl (metalaxyl); famoxadone (famoxadone); benziothiazolinone (benziothiazolinone); zoxamide (zoxamide); fluazinam (fluazinam); pyraclostrobin (pyraclostrobinin); azoxystrobin (azoxystrobin); oxathiapiprolin (oxathiapirolin); aluminum ethyl phosphate (fosetyl aluminum); copper nonyl phenolsulfonate; propineb (propineb); zineb (zineb); enestroburin (enestroburin); bupirimate (enestroburin); ethirimol (ethirimol); kresoxim-methyl (kresoxim-methyl); isopyrazam (isopyrazam); fluxapyroxad (fluxapyroxad); difenoconazole (difenoconazole); boscalid (boscalid); biguanide trioctylphenyl sulfonate (iminoctadine trialbisilate); polyoxins (polyoxins); wuyiencin (astromicin); berberine (berberine); thiophanate methyl (thiophanate methyl); mandipropamid (mandipropamid).
The mass ratio of the active component 1) to the active component 2) is 1:50-50: 1.
The mass ratio of the active component 1) to the active component 2) is 1:25-25: 1.
The mass ratio of the active component 1) to the active component 2) is 1:10-10: 1.
The mass ratio of the active component 1) to the active component 2) is 1:5-5: 1.
The germicidal composition also includes a surfactant and/or a filler.
The content of the active component 1) and the active component 2) accounts for 5% -90% of the bactericidal composition.
The content of the chemical active component 1) and the active component 2) accounts for 10-80% of the bactericidal composition.
The content of the active component 1) and the active component 2) accounts for 20-60% of the bactericidal composition.
The bactericide is used for preventing and treating downy mildew, late blight, epidemic disease, damping off, powdery mildew, rust disease, anthracnose, root rot and black shank of vegetables, fruits and field crops.
The bactericide is used for preventing and treating downy mildew, powdery mildew and epidemic disease of vegetables, fruits and field crops.
The bactericide composition is used for preventing and treating downy mildew, late blight, epidemic disease, damping off, powdery mildew, rust disease, anthracnose, root rot and black shank of vegetables, fruits and field crops.
The bactericide composition is used for preventing and treating downy mildew and epidemic powdery mildew on vegetables, fruits and field crops.
The formulation of the bactericidal composition is missible oil, aqueous suspension, oil suspension, wettable powder, water dispersible granules, microemulsion, aqueous emulsion, microcapsule, dry suspension or suspoemulsion. The formulations of the invention can be prepared by mixing the active compounds with the customary additives in a known manner. Such as conventional extenders as well as solvents or diluents, emulsifiers, dispersants, and/or binders or fixatives, wetting agents, water repellents, if desired siccatives and colorants, stabilizers, pigments, defoamers, preservatives, thickeners, water and other processing aids.
The compositions of the invention have good plant tolerance at the concentrations required for controlling plant diseases, which allows the treatment of aerial parts of plants, in vitro propagation plants (propagationstock), seeds and soils. The compositions of the invention may also be applied foliar or used for seed coating. The invention also provides seeds coated with the composition of the invention.
The compositions according to the invention have effective microbicidal activity and can be used for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection or in the protection of materials. We have found that the simultaneous, i.e. joint or separate, or sequential application of compound a and active compound B leads to better control of harmful fungi, bacteria (synergistic mixtures) than the individual compounds. At the same time, the combined or separate application of compound a and active compound B additively increases the bactericidal activity.
Mixtures of compound a and active compound B, or simultaneous, i.e. combined or separate use of compound a and active compound B, have excellent activity against a wide range of phytopathogenic fungi, in particular fungi selected from the class Ascomycetes (Ascomycetes), Deuteromycetes (Deuteromycetes), Oomycetes (Oomycetes) and Basidiomycetes (Basidiomycetes).
Mixtures of compound A and active compound B, or simultaneous, i.e. combined or separate, use of compound A and active compound B can be used for controlling phytopathogenic bacteria. Such as Pseudomonas (Psedomonas), Rhizobiaceae (Rhizobiaceae), Enterobacter (Enterobacteriaceae), Corynebacterium (Cornebacteriaceae), and Streptomyces (Streptomyces).
The following pathogens which cause fungal and bacterial diseases, which are included under the generic names mentioned above, can be mentioned by way of example and without limitation: flavobacterium species, such as rice white leaf cumquat (Xanthomonas campestris pv. oryzae); pseudomonas species, such as Pseudomonas syringae Cucumis sativus var (Pseudomonas syringae, Lachrymans); erwinia species, such as Erwinia amylovora (Erwinia amylovora); pythium species, such as Pythium ultimum; phytophthora (Phytophthora) species, such as Phytophthora infestans (Phytophthora infestans); pseudoperonospora species (Pseudoperonospora), such as Pseudoperonospora praecox (Pseudoperonospora humuli) or Pseudoperonospora cubensis (Pseudoperonospora cubensis); peronospora species (Plasmopara), such as, for example, Plasmopara viticola (Plasmoparaviticola); peronospora species (Bremia) such as, for example, peronospora lactucae (Bremia lactucae); peronospora species, such as Peronospora pisi (Peronospora pisi) or Peronospora crucifer (p. brassicae); powdery mildew species (Erysiphe), such as Erysiphe graminis (Erysiphe graminis); monocapsulata species (Sphaerotheca), such as, for example, balsamine monocapsula (Sphaerotheceaf uliginea); sphaerotheca (Podosphaera) species, such as Podosphaera leucotricha (Podosphaera leucotricha); venturia species (Venturia), such as apple scab (Venturian aqualis); pyrenophora species, such as Pyrenophora teres (Pyrenophora) or Pyrenophora graminea (P.graminea) (conidia form: Drechslera, Syn: Helminthosporium); cochliobolus (Cochliobolus) species, such as Cochliobolus graminis (Cochliobolus sativus) (conidia form: Drechslera, Syn: Helminthosporium); strains of the genus unicellular (Uromyces), such as, for example, Ruscus verrucosa (Uromyces-apendiculus); puccinia (Puccinia) species, such as Puccinia recondita (Puccinia recondita); sclerotinia species, such as Sclerotinia sclerotiorum (sclerotiorum); tilletia species, such as Tilletia tritici (Tilletia) tritici; ustilago (Ustilago) species, such as Ustilago nuda (Ustilago nuda) or Ustilago avenae (Ustilago avenae); pellicularia (Pellicularia) species, such as, for example, Pellicularia zoysiana (Pellicularia sakii); pyricularia species (Pyricularia), such as Pyricularia oryzae (Pyricularia oryzae); fusarium (Fusarium) species, such as Fusarium flavum (Fusarium culmorum); botrytis (Botrytis) species, such as Botrytis cinerea (Botrytis cinerea); septoria species (Septoria), such as Septoria nodorum (Septoria nodorum); leptosphaeria (Leptosphaeria) species, such as Leptosphaeria nodorum; cercospora (Cercospora) species, such as Cercospora grayani (Cercosporacananescens); alternaria (Alternaria) species, such as Alternaria brassicae (Alternaria brassicae); pseudocercospora species (Pseudocercospora), such as, for example, Rhizoctonia cerealis (Pseudocercospora herpotrichoides); (ii) a species of the genus Phakopsora (Phakopsora), such as Phakopsora pachyrhizi (Phakopsora hyrhizoizi) and Phakopsora meibomiae (Phakopsora meibomiae); and Rhizoctonia species (Rhizoctonia), such as Rhizoctonia solani (Rhizoctonia). The compositions of the invention are particularly suitable for controlling the following plant diseases:
alternaria (Alternaria) on vegetables, oilseed rape, sugar beet and fruits and rice, Saccharomycosis (Aphanomyces) on sugar beet and vegetables, Helminthosporium planiformis (Bipolaris) and Helminthosporium endothecium (Drechslera) in corn, cereals, rice and lawn, Blumeria graminis (powdery mildew) on cereals, Botrytis cinerea (Botrytis cinerea) (gray mold) on strawberries, vegetables, flowers and vines, Bremia lactucae (Bremia lactucae) on lettuce, Cercospora (Cercospora) on corn, soybean, rice and sugar beet, Cochliomyces (Cochliobolus) on corn, cereals, Cochliospora oryzae (Cochliobacter) on rice (for example Cochliobolus sativus on cereals), Cochliospora colletotrichum (Cochliospora) on rice, Helminthosporium and Helminthosporium on corn (Helminthosporium ) on cereals and Helminthosporium, Helminthosporium on corn (Drechelongassum), erysiphe cichororaceae and Sphaerotheca fuliginea (Sphaerotheca fuliginea), Fusarium (Fusarium) and Verticillium (Verticillium) on various plants, Populus graminis (Gaeumannomyces graminis) on cereals and Rice (Gibberella) on cereals and rice (e.g.Gibberella fujikuroi on rice), Grating dyeing complex on rice (Grating complex), Helminthosporium (Helminthosporium) on maize and rice, Michrodococcus nivale on cereals, Mycosphaerella on cereals, Musae and peanuts (Mycosphaerella) on cereals, Phytophthora sojae (Kopysora pauci) and Phachys cinerea (Phachytrispora), Phomopsis cinerea (Phomopsis citri), Phomopsis grisea and Phomopsis on potatoes (Phosporulata), Phomopsis grisea and Phomopsis on potatoes (Phomopsis graminis), Phomopsis cinerea (Phomopsis cinerea) and Phomopsis (Phomopsis, pseudoperonospora Pseudoperonospora (Pseudoperonospora) on hops and cucurbits, Puccinia (Puccinia) on cereals and corn, Pyrenophora (Pyrenophora) on cereals, Pyricularia oryzae (Pyricularia 0. eta. zae) on rice, Fucus carolina (Corticillus sakii), Sclerotium oryzae (Sarocladium oryzae), sheath rot disease of rice (S.aetenutatum), Ustilago oryzae (Entyloma oryzae), Pyricularia oryzae (Pyricularia grisea) on lawn and cereals, Pythium species on lawn, rice, corn, cotton, oilseed rape, sunflower, sugarbeet, Pythium (Pythium) on vegetables and other plants, cotton, rice, potato, lawn, corn, oilseed rape, sugarbeet, Rhizoctonia (Rhizoctonia) on vegetables and other plants, Rhizoctonia (Rhizoctonia) on sunflower and Rhizoctonia (Rhizoctonia) on wheat and grapevine (Rhizoctonia) on cereals and corn, Rhizoctonia (Rhizoctonia) on cereals and corn, the genus Setospora on maize and lawn, the genus Sphacelotheca reilinia on maize, the genus Leuconostoc rhizogenes (Thievaniopsis) on soybean and cotton, the genus Tilletia on cereals (Tilletia), the genus Ustilago (Ustilago) on cereals, maize and sugar beets, the genus Venturia (Venturia) on apples and pears (scab).
The compositions of the invention are particularly important for controlling a large number of fungi in various crops such as cotton, vegetable varieties (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grasses, oats, bananas, coffee, maize, fruit varieties, rice, rye, soybeans, grapevines, wheat, ornamentals, peanuts, oilseed rape, sugar cane and various seeds.
The compositions according to the invention are particularly suitable for controlling phytopathogenic fungi from the group of cereal fungi (Blumeia graminis) (powdery mildew), from the group of Cucurbitaceae plants (Erysiphe cichororaceae) and Sphaerotheca fuliginea (Sphaerotheca fuliginea), from the group of apple powdery mildew (Podosphaera leucotricha) in apples, from the group of Uncaria botrytis (Uncinula necator) in grapevine, from the group of Puccinia (Puccinia) in cereals, from the group of Rhizoctonia solani (Rhizoctonia) in cotton, rice and lawn, from the group of Ustilago (Utilio) in cereals and sugar cane, from the group of Venturia melanosporum (Venturia inalis) (Venturia scabra), from the group of Helminthosporium (Helminthosporium) in cereals and sugar cane, from the group of wheat (Torulopsis rosea), from the group of wheat (Septoria graminis, from the group of Bochybotrytis cinerea) and from the group of Gracilaria (Bochybotrytis cinerea) in vegetables, from the group of Bochybotrytis cinerea (Bochylotia (Bochylotea), from the genus Bochybotrytis, pyricularia oryzae (Pyricularia oryzae) in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola (Plasmopara viticola) in grapevines, Pseudoperonospora Pseudoperonospora (Pseudoperonospora) in hops and cucumbers, Alternaria (Alternaria) in vegetables and fruits, Mycosphaera (Mycosphaera) in bananas, and Neurospora (Fusarium) and Verticillium (Verticillium).
The composition is especially suitable for preventing and treating downy mildew, powdery mildew, epidemic disease, damping-off, rust disease and anthracnose.
The compositions of the present invention exhibit low toxicity and excellent plant tolerance. All plants and plant parts can be treated according to the invention. Plants are to be understood as meaning all plants and plant populations, for example desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which are obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants, but also including the plant varieties which are protected or not protected by plant breeders' rights. Plant parts are to be understood as meaning all parts of the ground and underground and plant organs of plants, such as shoots, leaves, flowers and roots, examples which may be mentioned being leaves, needles, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. Plant parts also include harvests, as well as vegetative and generative plant propagation material, such as seedlings, tubers, rhizomes, cuttings and seeds.
Depending on the plant species or plant cultivars, their location and growth conditions (soil, climate, vegetation period, nutrition), the treatment according to the invention may also produce superadditive (synergistic) effects. This can lead to effects which are more than actually expected, for example a reduction in the application rate and/or a widening of the spectrum of action and/or an increase in the activity of the compositions according to the invention, an improvement in the growth of the plants, an increase in the tolerance to high or low temperatures, an increase in the tolerance to drought or to salt content in water or soil, an increase in the flowering performance, easier harvesting, accelerated maturation, increased yield, an increase in the quality and/or the nutritional value of the harvested products, an improvement in the storage properties and/or the processability of the harvested products.
According to the invention, the treatment of plants and plant parts with the compounds is carried out directly according to conventional treatment methods, such as dipping, spraying, evaporation, fogging, scattering, painting on, or by treating the environment, habitat or storage space in which they are located; for propagation material, in particular seeds, one or more coatings may also be applied.
Preferred methods of application are application to the aerial parts of the plants, especially foliar application; the number of applications and the application rate depend on the biological and climatic survival conditions of the target microorganisms. However, the active ingredient may also reach the plant body through the root system via soil or water, whereby the locus can be watered with a liquid preparation or the substance can be incorporated into the soil in solid form. The compositions of the invention may also be applied to cereal seeds in seed treatment, whereby the tubers or grains may be soaked in a liquid formulation of each active ingredient in sequence, or wrapped with a wet or dry formulation that has been mixed.
The active ingredient is incorporated into the locus of the plant, for example in the form of granules (soil application), or it can enter the interior of the plant via the root system (systemic action). The soil or culture medium of the plant used in the practice of the method of the present invention is a support capable of rooting and growing a crop, and includes, for example: examples of the raw material include sand, pumice, vermiculite, diatomaceous earth, agar, gel, polymer, asbestos, wood chips, and bark.
In the preparation of the mixtures, preference is given to using the active compounds in pure form, if desired in admixture with other active compounds against harmful fungi or other pests such as insects, arachnids or nematodes or herbicidal or growth-regulating active compounds or fertilizers as further active ingredients.
In a preferred embodiment of the invention, mixtures of compound a and active compound B are used. Under certain conditions, it may be advantageous to combine compound a with two or more active compounds B.
The compound A and the active compound B are generally used in a weight ratio of from 100:1 to 1:100, preferably from 50:1 to 1:50, preferably from 25:1 to 1:25, preferably from 10:1 to 1:10, in particular from 5:1 to 1: 5.
Depending on the type of compound and the desired effect, the application rates of the mixtures according to the invention are from 5 to 2000g/ha, preferably from 50 to 900g/ha, in particular from 50 to 750 g/ha.
Accordingly, the application rate of compound A is generally from 1 to 1000g/ha, preferably from 10 to 900g/ha, in particular from 20 to 750 g/ha.
In the seed treatment, for example by dusting, coating or soaking the seed, the application rate of the mixture is generally from 1 to 1000g per 100kg of seed, preferably from 1 to 750g per 100kg, in particular from 5 to 500g per 100 kg.
The method for controlling harmful fungi is carried out by spraying or dusting the seeds, plants or soil before or after the sowing of the plants or before or after the emergence of the plants, with the application of compound a and active compound B or a mixture of compound a and active compound B separately or in combination.
The mixtures according to the invention or compound a and active compound II can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of use depends on the particular intended purpose, in each case ensuring a fine and homogeneous distribution of the compounds of the invention.
The formulations are prepared in a known manner, for example by mixing the active compounds with solvents and/or carriers, if desired using emulsifiers and dispersants. Suitable solvents/auxiliaries for this purpose are mainly:
water, aromatic solvents (e.g. Solvesso products, xylene), paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones (e.g. cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (ethylene glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, it is also possible to use solvent mixtures.
Carriers such as ground natural minerals (e.g. kaolin, clay, talc, chalk) and ground synthetic minerals (e.g. highly dispersed silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.
Suitable surfactants used are alkali metal salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkaline earth metal and ammonium salts, alkylaryl sulphonates, alkyl sulphates, alkyl sulphonates, fatty alcohol sulphates, fatty acids and sulphated fatty alcohol glycol ethers, and also condensates of sulphonated naphthalenes and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulphonic acids with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dustable products can be prepared by mixing or simultaneously grinding the active substance with a solid carrier.
Particles such as coated particles, impregnated particles and homogeneous particles can be prepared by adhering the active compound to a solid support. Examples of solid carriers are mineral earths such as silica gel, silicates, talc, kaolin, activated clays (attacalay), limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium oxide; a ground synthetic material; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of vegetable origin such as cereal flour, bark powder, wood flour and nutshell flour, cellulose powder and other solid carriers.
The formulation for seed treatment may additionally comprise binders and/or gelling agents and, if appropriate, colorants.
The formulations generally comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of active compound. The active compounds are used in a purity of 90 to 100%, preferably 95 to 100%.
For seed treatment, the formulations give, after 2-to 10-fold dilution, active compound concentrations in the ready-to-use preparations of 0.01 to 40% by weight, preferably 0.1 to 30% by weight.
For the treatment of soils, the application rate of the active ingredient is generally between 0.1 and 10000g/ha, preferably between 1 and 5000 g/ha.
The above-mentioned dosages are only typical exemplary dosages, and the person skilled in the art will adjust the application rate in the actual application according to the actual circumstances and needs, in particular according to the nature of the plants or crops to be treated and the severity of the germs.
The compositions of the invention may also be administered in combination with other active ingredients, for example to broaden the spectrum of activity or to prevent the development of resistance. Such as fungicides, bactericides, attractants, insecticides, acaricides, nematicides, growth regulators, herbicides, safeners, fertilizers or semiochemicals and the like.
The invention has the beneficial effects that: through research, the compound A, namely 4-chloro-2- (1, 1-dimethylethyl) -5- [ [ [4- (1, 1-dimethylethyl) phenyl ] methyl ] thio ] -3(2H) -pyridazinone is found to have good control effect on downy mildew, late blight, epidemic disease, damping-off, powdery mildew, rust disease, anthracnose, root rot, phytophthora parasitica and the like of vegetables, fruits and field crops. In order to avoid the defect of drug resistance caused by single use, the compound A and bactericides with different action mechanisms are reasonably mixed, so that the synergistic effect is remarkable, the control effect is improved, the application times and the dosage are reduced, the generation of germ resistance is avoided, the generation speed of the drug resistance is delayed, and the problems of resistance and the like in the application process of a single pesticide can be solved.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
1. Product diluted with water
A) Water-soluble concentrate (SL, LS, GW, PA)
10 parts by weight of the mixture according to the invention are dissolved in 90 parts by weight of water or water-soluble solvent. Alternatively, a wetting agent or other auxiliary agent is added. The active compound is dissolved by dilution with water. In this way, a formulation with an active compound content of 10% by weight is obtained.
B) Dispersion Concentrate (DC)
20 parts by weight of the mixture according to the invention are dissolved in 70 parts by weight of cyclohexanone and 10 parts by weight of a dispersant, such as polyvinylpyrrolidone, are added. Dilution with water gives a dispersion. The active compound content was 20% by weight.
C) Emulsifiable Concentrates (EC)
15 parts by weight of the mixture according to the invention are dissolved in 75 parts by weight of xylene and calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight) are added. Diluting with water to obtain emulsion. The active compound content of the formulation was 15% by weight.
D) Emulsion (EW, EO, ES, ME)
25 parts by weight of the mixture according to the invention are dissolved in 35 parts by weight of xylene and calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight) are added. The mixture was introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Diluting with water to obtain emulsion. The active compound content of the formulation is 25% by weight.
E) Suspension (SC, OD, FS, CS, SE, ZC, ZW, ZE)
In a stirred ball mill, 20 parts by weight of the mixture according to the invention are comminuted and 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or organic solvent are added to give a finely divided active compound suspension. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation was 20% by weight.
F) Water-dispersible and water-soluble granules (WG, SG, EG, ST, EP, WT, GE, DF)
50 parts by weight of the mixture according to the invention are finely ground and 50 parts by weight of dispersing and wetting agents are added and are made into water-dispersible or water-soluble granules by means of industrial devices, such as granulators, spray towers, fluidized beds. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 50% by weight.
G) Water-dispersible powder and water-soluble powder (WP, SP, SS, WS)
75 parts by weight of the mixture according to the invention are comminuted in a jet mill and 25 parts by weight of dispersant, wetting agent and silica gel are added. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation was 75% by weight.
H) Gel formulations
20 parts by weight of the inventive mixture, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or organic solvent are ground in a ball mill to give a fine suspension. Dilution with water gives a stable suspension with an active compound content of 20% by weight.
2. Product to be applied undiluted
I) Dustable powder (DP, DS)
5 parts by weight of the mixture according to the invention are finely ground and thoroughly mixed with 95 parts by weight of finely divided kaolin. This gives a dustable product with an active compound content of 5% by weight.
J) Granules (GR, FG, GG, MG)
0.5 part by weight of the mixture according to the invention is finely ground and combined with 99.5 parts by weight of a carrier. Current processes are extrusion, spray drying or fluidized bed processes. This gives granules which are applied undiluted and have an active compound content of 0.5% by weight.
K) ULV solutions (UL)
10 parts by weight of the mixture according to the invention are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product which is applied undiluted and has an active compound content of 10% by weight.
For seed treatment, water-soluble concentrates (LS), suspensions (FS), dustable powders (DS), water-dispersible and water-soluble powders (WS, SS), Emulsions (ES), Emulsifiable Concentrates (EC) and Gel Formulations (GF) are generally used. These formulations can be applied to the seed undiluted or preferably diluted. Application may be carried out prior to sowing.
FS formulations for seed treatment are preferably used. Such formulations generally comprise from 1 to 800g of active compound/L, from 1 to 200g of surfactant/L, from 0 to 200g of antifreeze agent/L, from 0 to 400g of binder/L, from 0 to 200g of colorant/L and a solvent, preferably water.
Analogous formulations A to K of Compound A or active Compound B comprise the respective active compound in corresponding amounts. They are usually mixed directly before application in the course of dilution to the ready-to-use active compound concentration (tank mix).
The concentration of the active compound in the ready-to-use formulation can vary within wide limits. They are generally from 0.0001 to 10%, preferably from 0.01 to 1%.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom (e.g. directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials or granules for spreading), by means of spraying, atomizing, dusting, spreading or pouring. The form of use depends entirely on the intended purpose; it is intended to ensure in each case the best possible distribution of the active compounds according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by addition of water. To prepare emulsions, pastes or oil dispersions, the substances can be homogenized in water, either directly or after dissolution in oil or solvent, with the aid of wetting, viscosity-increasing, dispersing or emulsifying agents. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and which are suitable for dilution with water.
The active compounds can also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations which comprise more than 95% by weight of active compound, or even to apply active compound without additives.
Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other pesticides or bactericides can be added to the active compounds, if desired only immediately before use (tank mix). These agents are generally mixed with the composition of the invention in a weight ratio of 1:100-100:1, preferably 1:10-10: 1.
The compounds A and B or the mixtures or corresponding formulations are applied by treating the harmful fungi, bacteria with a fungicidally effective amount of the mixture or, in the case of separate application, the compounds A and B, the application time being chosen either before or after infestation by the harmful fungi, bacteria.
Application examples
The fungicidal effect of the compounds and mixtures was demonstrated by the following tests:
the synergistic effect of the compositions according to the invention on harmful fungi is further illustrated by the following examples, to which, however, the invention is in no way restricted. The active components are the compound A and other fungicide active components B in the bactericidal composition.
The test method and the evaluation method are as follows:
the expected effect of a particular combination of two active compounds can be achieved using the so-called "Colby's formula" (cf. S.R.Colby, "cutting synergistic diagnostic responses of pharmacological compositions", Weeds1967, 15, 20-22)
Is calculated as follows if
X is the activity when active compound A is used in an amount of α g/ha or at a concentration of α ppm;
y is the activity when active compound B is used in an amount of β g/ha or at a concentration of β ppm, expressed as a percentage of the untreated control;
e is the activity when using the active compounds A and B in amounts of α and β g/ha or at concentrations of α and β ppm;
If the actual observed activity is greater than the expected activity, the composition is superadditive, i.e., has a synergistic effect.
EXAMPLE 1 control of cucumber downy mildew test
The cucumber seedling at the two-leaf stage of the potted plant of the variety 'Shandong Mici' is treated by spraying with an aqueous solution (the concentration is described below) of an active component, 24 hours later, the cucumber downy mildew spore suspension is inoculated on the cucumber leaf, then the cucumber leaf is cultured in a climate chamber with the temperature of 18 +/-1 ℃ and the relative humidity of 90 +/-5%, and the development degree of germ infection on the leaf is measured after 3 days. The results of the activity data for the individual active components and for the composition according to the invention for cucumber downy mildew are shown in tables 1 and 2.
The results show that the actual control effect value of the composition is larger than the theoretical control effect value, and the composition has a synergistic effect in the range of the experimental mixture ratio.
TABLE 1 controlling effect of the active ingredients alone on cucumber downy mildew
TABLE 2 controlling effect of the composition of the present invention on cucumber downy mildew
Example 2 test for controlling cucumber powdery mildew
Selecting cucumber potted seedlings (variety: Xintai Mici) with uniform growth and same leaf age, spraying the leaves on the crop spray according to the designed dosage, and arranging a blank control without medicament. After 24 hours, the seeds were inoculated with pathogenic bacteria, and then transferred to a greenhouse for normal management, and the seeds were cultured under culture conditions (temperature: 23-28 ℃ in the day and 18-20 ℃ in the night) for 8 days, and then the results were investigated. And investigating the development degree of pathogen infection of each leaf. The results of the data on the individual active ingredients and the activity of the compositions according to the invention for controlling cucumber powdery mildew are shown in table 3 and table 4.
The results show that the actual control effect of the composition is greater than the theoretical control effect, and the composition shows a synergistic effect in the range of the experimental mixture ratio.
TABLE 3 preventive effect of individual active ingredients on cucumber powdery mildew
TABLE 4 Activity of the compositions of the invention
Through a large number of tests, the composition A and a plurality of different components B such as dimethomorph, flumorph, fluopicolide, zoxamide, cyazofamid, chlorothalonil, mancozeb, benziothiazolin, fosetyl aluminum, cupprionan, cymoxanil, pyraclostrobin, fluorothiazolopyrone and the like are mixed at a ratio of 1:10-10:1 to prevent and treat the tomato late blight, and the composition has a synergistic effect. Has good synergistic effect on the prevention and treatment of potato late blight.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A fungicide composition comprising, as active ingredients, in synergistically effective amounts:
a compound A: 4-chloro-2- (1, 1-dimethylethyl) -5- [ [ [4- (1, 1-dimethylethyl) phenyl ] methyl ] thio ] -3(2H) -pyridazinone;
and compound B: wuyimycin; the mass ratio of the compound A to the compound B is 1:10-10: 1.
2. The germicide composition according to claim 1, characterized in that: the mass ratio of the compound A to the compound B is 1:1-4: 1.
3. The germicide composition according to claim 2, characterized in that: the mass ratio of the compound A to the compound B is 1:1, 2:1 or 4: 1.
4. The germicide composition according to claim 1, characterized in that: the biocide composition further comprises a surfactant and/or a filler.
5. The germicide composition according to claim 4, wherein: the content of the compound A and the compound B accounts for 5 to 90 percent of the bactericide composition.
6. The germicide composition according to claim 5, wherein: the content of the compound A and the compound B accounts for 10-80% of the bactericidal composition.
7. The germicide composition according to claim 6, wherein: the content of the compound A and the compound B accounts for 20-60% of the bactericidal composition.
8. Use of a fungicide composition according to any one of claims 1 to 7, characterized in that: the bactericide composition is used for preventing and treating downy mildew, late blight, epidemic disease, damping off, powdery mildew, rust disease, anthracnose, root rot and black shank of vegetables, fruits and field crops.
9. Use of a fungicide composition according to claim 8, characterized in that: the bactericide composition is used for preventing and treating downy mildew and epidemic powdery mildew on vegetables, fruits and field crops.
10. Use of a fungicide composition according to any one of claims 1 to 7, characterized in that: the formulation of the bactericidal composition is missible oil, aqueous suspension, oil suspension, wettable powder, water dispersible granules, microemulsion, aqueous emulsion, microcapsule, dry suspension or suspoemulsion.
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CN112088889B (en) * | 2019-06-18 | 2023-08-04 | 东莞市东阳光菌阳氢专利农药有限公司 | Composition containing Pyridachlorometyl and zinc thiazole |
CN110250190A (en) * | 2019-07-22 | 2019-09-20 | 东莞东阳光科研发有限公司 | A kind of composition, preparation and its application, preparation method |
CN110301436A (en) * | 2019-08-13 | 2019-10-08 | 福建拓烯新材料科技有限公司 | A kind of microcapsule formulations composition and preparation method thereof |
CN110506747A (en) * | 2019-08-28 | 2019-11-29 | 浙江海正化工股份有限公司 | Using cyproconazole and copper 8-hydroxyquinolinate as the composition pesticide of active constituent and its preparation and application |
CN110692628B (en) * | 2019-11-08 | 2021-06-25 | 广西壮族自治区农业科学院 | Downy mildew prevention and treatment method for downy mildew of downy grapes, prevention and treatment agent and preparation method of prevention and treatment agent |
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CN113142231A (en) | 2021-07-23 |
CN113142223A (en) | 2021-07-23 |
CN113142224A (en) | 2021-07-23 |
CN113142221A (en) | 2021-07-23 |
CN113142219A (en) | 2021-07-23 |
CN109169678A (en) | 2019-01-11 |
CN113142226A (en) | 2021-07-23 |
CN113142236A (en) | 2021-07-23 |
CN113142235A (en) | 2021-07-23 |
CN113142218A (en) | 2021-07-23 |
CN113040155A (en) | 2021-06-29 |
CN113142222A (en) | 2021-07-23 |
CN113142227A (en) | 2021-07-23 |
CN113142225A (en) | 2021-07-23 |
CN113142230A (en) | 2021-07-23 |
CN113142220A (en) | 2021-07-23 |
CN109169678B (en) | 2021-03-26 |
CN113040157A (en) | 2021-06-29 |
CN113142229A (en) | 2021-07-23 |
CN113040156A (en) | 2021-06-29 |
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